Post on 09-Sep-2019
Environment Protection Engineering
Vol 43 2017 No 1
DOI 105277epe170110
EWA SZAREK-GWIAZDA1 DARIUSZ CISZEWSKI2
VARIABILITY OF HEAVY METAL CONCENTRATIONS
IN WATERS OF FISHPONDS AFFECTED BY THE FORMER
LEAD AND ZINC MINE IN SOUTHERN POLAND
The fluctuations of heavy metal (Cd Pb Zn Mn and Fe) concentrations and physicochemical parame-
ters of water were studied for five fishponds located in the Matylda catchment affected by the former Pb and
Zn ore mine in the Upper Silesian Industrial Region southern Poland Generally metal concentrations in
dissolved phase in pond water were low for most of the year but their drastic increases were periodically
observed (up to Cd 58 Pb 1473 Zn 8003 Mn 9878 and Fe 25328 microgmiddotdmndash3) The factors determining
metal concentrations in the pond water have been discussed
1 INTRODUCTION
Metal mining and processing cause usually severe contamination of nearby lands
Metal contamination of soils and sediments in such areas is an important problem even
many years after cessation of the ore processing [1ndash3] Heavy metal concentrations in
contaminated sediments [1ndash4] exceeding several times the values of toxic effect thresh-
old (TET) (Cd 3 Pb 170 and Zn 540 microgmiddotgndash1
according to EC and MENVIQ [5]) above
which sediments are considered heavily polluted and having detrimental effects on sed-
iment-fed organisms For cleaning metal-polluted sediments and soils in situ or ex situ
phytoremediation is frequently used [6]
Metals can be remobilized from contaminated sediments under favorable environ-
mental conditions (pH redox potential frequent resuspension) [7 8] Mobilization of
heavy metals from sediments due to complex biological physicochemical and hydro-
_________________________
1Institute of Nature Conservation Polish Academy of Sciences ul Mickiewicza 33 31-120 Cracow
Poland corresponding author e-mail szarekiopkrakowpl 2AGH-University of Science and Technology ul Mickiewicza 30 30-059 Cracow Poland
122 E SZAREK-GWIAZDA D CISZEWSKI
logical processes [1 9] is conducive to appearance of high concentrations of heavy met-
als in water and might cause a serious environmental threat Therefore it is necessary to
investigate the fate of trace metals in hydrosystems impacted by mining wastes
Olkusz and Chrzanoacutew lead-zinc mining areas in the Upper Silesian Industrial Re-
gion in Southern Poland provide a unique example of the industrial impact on the
aquatic environment The history of zinc-lead mining activities which began in this area
in 13th century lasts up today whereas the Matylda Stream itself situated in this area
received mine waters from the Pb-Zn mine Matylda in Chrzanoacutew in 19th and 20th cen-
turies Even though the mine has been closed for over 40 years sediments of the
Matylda Stream and fishponds built already in 19th century in order to utilize mine
water situated in the middle course of the stream are still heavily contaminated with
Pb Zn and Cd [4] Despite this the structure of biotic elements (algae zooplankton) in
the fishponds during the vegetation season is fairly rich in species [10] However ge-
nom alteration of some Chironomidae species living in the sediment of the Matylda
Stream was related to high metal contamination [11] The decline of the macrophyte
species (Myriophyllum spicatum) in one of the fishponds [4] after periodical increase in
the concentrations of heavy metals in the pond water also indicated detrimental effect
of contaminants there
The aim of the present paper was to study the variability of the dissolved phase of
trace metals and macroions in water of fishponds situated in the middle part of the
Matylda catchment affected by effluents from the former lead and zinc mine
2 MATERIALS AND METHODS
Study area and sampling The Matylda catchment (Fig 1) is situated in the Upper
Silesian Industrial Region in southern Poland It was affected by the former lead and
zinc ore mine in Chrzanoacutew which operated from 1850 to 1973 During this time the
Matylda stream received variable amounts of mine water which exceed natural river
discharge by even 100 times [4] In the time of mine operation groundwater seepage
combined with surface drainage caused pollution of sandy soils exceeding over 100
microgmiddotgndash1
of Cd 24 of Zn and 4 of Pb at surface or subsurface soil horizons and reach-
ing at least 60 cm in depth [12] Since 1973 the Matylda stream with the discharge of
about 10 dm3 s
ndash1 in its middle reach has drained a small catchment of a dozen or so
square kilometers
Five fishponds were investigated in the Matylda catchment (Fig 1) The Upper
Pond (UP) was located in the upper part of the catchment closest to the former metal
mine A cascade of three ponds in the middle part of the catchment consists of an upper
Small Pond (SP) a middle Medium Pond (MP) and the largest Lower Pond (LP) The
first of the cascade of ponds (SP) was directly supplied with water from the Matylda
Stream One more lower pond (LoP) was situated in the lower part of the catchment
Heavy metal concentrations in waters affected by the former lead and zinc mine 123
and supplied both with the waters from the cascade of ponds and relatively unpolluted
tributary The depth of the ponds reaches 2 m During the pond operation a part of
sediments was removed from the UP and LoP ponds whereas in the LP sediments were
shifted with a bulldozer toward the southeast banks of the pond Sediments of the MP
and SP ponds were intact
Fig 1 Locations of the research area and sampling points a) dykes and roads b) dykes
c) sampling points UP ndash upper pond SP ndash small pond MP ndash middle pond LP ndash large pond
LoP ndash lower pond 1 ndash highway 2 ndash main roads 3 ndash forest roads 4 ndash railways
5 ndash fish ponds 6 ndash forests 7 ndash closed Matylda mine 8 ndash built-up area
Samples of water (surface layer) were collected from the central and near-bank
parts of the SP MP LP and LoP ponds and from the UP only of its central part The
samples were taken monthly from April 2009 to March 2010 except of July 2009
(all ponds) and September 2009 (central parts of SP MP LP and LoP) The sampling
on dry spring of 2009 (April and May) was followed by wet early summer with rainfalls
in June exceeding a multi-year average by 150 The following August September and
October were warmer and dryer than average (rainfalls of 50ndash75 of norm) Soon after
the sampling in October rains and snowfall of about 60 mm raised water level both in
ponds and in their tributaries Sampling in November represented wet period with low
temperatures reducing evaporation Winter started at the end of December and sampling
in January was preceded by monthly period of frosts and accretion of ice cover to the
thickness of 10ndash15 cm Sampling was finished at the end of March after rapid snow
melting preceded by over one month of temperatures fluctuated about 0 degC A perma-
nent ice cover lasted until the end of March In the collected samples the following
124 E SZAREK-GWIAZDA D CISZEWSKI
parameters were determined pH conductivity dissolved oxygen anions (Clndash SO4
2ndash
HCO3ndash NO3
ndash) and cations (Na
+ K
+ Ca
2+ Mg
2+ NH4
+) BOD5 organic matter (LOI) and
concentrations of heavy metals (Cd Pb Zn Mn and Fe)
Physicochemical analysis Conductivity and pH were determined using WTW
(Multi 340 and SET 2) apparatus whereas dissolved oxygen and BOD5 by the Winkler
method In order to analyze the content of anions and cations (heavy metals as well)
water samples were filtered through 045 μm pore-sized syringe filters into a polyeth-
ylene container The contents of inorganic ions (Clndash SO4
2ndash HCO3
ndash NO3
ndash Na
+ K
+ Ca
2+
Mg2+
NH4+) were determined within 48 h using ion chromatography (DIONEX ICS
1000 and IC DX 320) For the metal analysis samples of water were acidified to pH lt 2
with ultrapure HNO3 The concentrations of Zn Cd Pb Fe and Mn were measured with
an inductively coupled plasma mass spectrometer (Perkin Elmer ELAN 6100) The or-
ganic matter was determined as losses on ignition (LOI) at 550 degC
The differences in the heavy metal concentrations in water between the studied
ponds were analyzed using the KruskalndashWallis test while those within one pond be-
tween its central and coastal parts by the Wilcoxon test The relationships between the
concentrations of heavy metals and the values of physicochemical parameters were de-
termined by the Spearman correlation
3 RESULTS
31 PHYSICOCHEMICAL PARAMETERS OF WATER
The values of physicochemical parameters in the studied ponds (median range) are
given in Table 1 The water of SP MP LP and LoP had pH of 70ndash97 while pH in UP
varied in the range of 49ndash76 During the most of the year the water of UP had acidic
reaction pH was significantly lower in UP than in MP and LP (Table 2) In all ponds
pH was usually higher in spring and summer and then decreased reaching the lowest
values in winter months (JanuaryndashMarch) (Fig 2)
The waters of SP MP LP and LoP were usually well oxygenated (gt8 mg O2middotdmndash3
)
while that of UP weakly oxygenated (lt4 mg O2middotdmndash3
) However a decrease in the amount
of dissolved oxygen below 4 mg O2middotdmndash3
appeared also periodically in the waters of SP and
LP in the summer autumn and winter months (Fig 2) The content of dissolved oxygen was
significantly lower in the water of UP than that of other ponds (Table 2)
The amounts of anions and cations varied among the studied ponds (Table 1) The
median values of conductivity Clndash SO4
2ndash HCO3
ndash Ca
2+ and Na
+ were the highest in the
water of SP (the first of the cascade of ponds directly supplied with waters from the
Matylda stream) while that of Mg2+
occurred in LP (the last of the cascade) The lowest
Heavy metal concentrations in waters affected by the former lead and zinc mine 125
median contents of major anions and cations (with the exception of K+) were found in
the water of UP (Table 1) Low values of studied anions and cations were also found in
LoP (supplied both with waters from the cascade of ponds and from the relatively un-
polluted tributary) Occasionally drastic increase in the contents of major anions and
cations appeared in the pond waters (UP in May and September in the central and near-
bank parts of SP in April and May Fig 3) which were not accompanied by high con-
centrations of heavy metals
The values of BOD5 (the content of easily degradable organic matter) varied in the
range 03ndash82 mg O2middotdmndash3
and the amount of LOI in the range 15ndash262 mgmiddotdmndash3
(Table 1)
The values of BOD5 and contents of LOI were similar in the studied ponds and increased
in different months Moreover the amount of nitrates was lower during growing season
and higher in autumn and winter months
T a b l e 1
Median (M) and range (R) values of physicochemical parameters and concentrations
of heavy metals in waters of the ponds situated in the Matylda catchment
Parameter UP SP MP LP LoP
M R M R M R M R M R
pH 63 49ndash76 75 70ndash85 79 70ndash89 83 70ndash97 74 70ndash86
Conductivity
microS middotcmndash1 2155
1100
ndash11250 4810
2590
ndash6360 4320
2450
ndash4900 4340
1400
ndash4880 3730 2570ndash4290
Dissolved O2
mgmiddotdmndash3 38 05ndash54 86 16ndash120 93 58ndash106 95 19ndash117 91 46ndash115
Clndash mgmiddotdmndash3 190 130ndash438 272 135ndash374 235 167ndash329 245 96ndash314 208 118ndash258
HCO3ndash mgmiddotdmndash3 481 93ndash4452 1519 591ndash2612 1342 694ndash2021 1298 418ndash1623 1252 636ndash1921
SO42ndash mgmiddotdmndash3 475 279ndash2301 802 461ndash1366 775 388ndash1114 753 207ndash987 486 256ndash753
Na+ mgmiddotdmndash3 85 28ndash290 138 90ndash197 123 69ndash170 125 42ndash161 108 69ndash132
K+ mgmiddotdmndash3 27 17ndash108 32 20ndash63 30 11ndash39 28 08ndash45 24 17ndash32
Ca2+ mgmiddotdmndash3 232 121ndash1523 602 305ndash868 523 274ndash664 520 163ndash645 451 315ndash542
Mg2+ mgmiddotdmndash3 50 22ndash428 135 64ndash239 119 49ndash160 138 30ndash150 106 64ndash123
NO3ndash mgmiddotdmndash3 063 005ndash285 215 003ndash1862 199 002ndash1010 076 002ndash1832 065 002ndash2228
NH4+ mgmiddotdmndash3 022 003ndash461 009 002ndash090 008 002ndash038 008 001ndash049 013 003ndash021
BOD5 mgmiddotdmndash3 20 03ndash34 29 03ndash64 32 10ndash82 19 03ndash58 21 05ndash53
LOI mgmiddotdmndash3 1110 680ndash1550 1210 520ndash1950 1170 610ndash2620 1240 150ndash1910 1110 680ndash1550
Cd gmiddotdmndash3 29 003ndash580 09 002ndash448 02 002ndash260 006 002ndash116 03 002ndash191
Pb gmiddotdmndash3 84 13ndash757 108 24ndash1473 46 16ndash180 55 11ndash1060 56 16ndash107
Zn gmiddotdmndash3 4836 646ndash8003 3444 137ndash7908 611 104ndash5615 258 26ndash2913 688 71ndash2894
Mn gmiddotdmndash3 1204 947ndash2878 853 134ndash9871 269 48ndash1906 197 37ndash878 1068 107ndash2935
Fe gmiddotdmndash3 8059 1644ndash25328 1715 20ndash11246 961 498ndash2975 598 13ndash11001 2513 670ndash6390
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower
pond LOI ndash loss of ignition
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
122 E SZAREK-GWIAZDA D CISZEWSKI
logical processes [1 9] is conducive to appearance of high concentrations of heavy met-
als in water and might cause a serious environmental threat Therefore it is necessary to
investigate the fate of trace metals in hydrosystems impacted by mining wastes
Olkusz and Chrzanoacutew lead-zinc mining areas in the Upper Silesian Industrial Re-
gion in Southern Poland provide a unique example of the industrial impact on the
aquatic environment The history of zinc-lead mining activities which began in this area
in 13th century lasts up today whereas the Matylda Stream itself situated in this area
received mine waters from the Pb-Zn mine Matylda in Chrzanoacutew in 19th and 20th cen-
turies Even though the mine has been closed for over 40 years sediments of the
Matylda Stream and fishponds built already in 19th century in order to utilize mine
water situated in the middle course of the stream are still heavily contaminated with
Pb Zn and Cd [4] Despite this the structure of biotic elements (algae zooplankton) in
the fishponds during the vegetation season is fairly rich in species [10] However ge-
nom alteration of some Chironomidae species living in the sediment of the Matylda
Stream was related to high metal contamination [11] The decline of the macrophyte
species (Myriophyllum spicatum) in one of the fishponds [4] after periodical increase in
the concentrations of heavy metals in the pond water also indicated detrimental effect
of contaminants there
The aim of the present paper was to study the variability of the dissolved phase of
trace metals and macroions in water of fishponds situated in the middle part of the
Matylda catchment affected by effluents from the former lead and zinc mine
2 MATERIALS AND METHODS
Study area and sampling The Matylda catchment (Fig 1) is situated in the Upper
Silesian Industrial Region in southern Poland It was affected by the former lead and
zinc ore mine in Chrzanoacutew which operated from 1850 to 1973 During this time the
Matylda stream received variable amounts of mine water which exceed natural river
discharge by even 100 times [4] In the time of mine operation groundwater seepage
combined with surface drainage caused pollution of sandy soils exceeding over 100
microgmiddotgndash1
of Cd 24 of Zn and 4 of Pb at surface or subsurface soil horizons and reach-
ing at least 60 cm in depth [12] Since 1973 the Matylda stream with the discharge of
about 10 dm3 s
ndash1 in its middle reach has drained a small catchment of a dozen or so
square kilometers
Five fishponds were investigated in the Matylda catchment (Fig 1) The Upper
Pond (UP) was located in the upper part of the catchment closest to the former metal
mine A cascade of three ponds in the middle part of the catchment consists of an upper
Small Pond (SP) a middle Medium Pond (MP) and the largest Lower Pond (LP) The
first of the cascade of ponds (SP) was directly supplied with water from the Matylda
Stream One more lower pond (LoP) was situated in the lower part of the catchment
Heavy metal concentrations in waters affected by the former lead and zinc mine 123
and supplied both with the waters from the cascade of ponds and relatively unpolluted
tributary The depth of the ponds reaches 2 m During the pond operation a part of
sediments was removed from the UP and LoP ponds whereas in the LP sediments were
shifted with a bulldozer toward the southeast banks of the pond Sediments of the MP
and SP ponds were intact
Fig 1 Locations of the research area and sampling points a) dykes and roads b) dykes
c) sampling points UP ndash upper pond SP ndash small pond MP ndash middle pond LP ndash large pond
LoP ndash lower pond 1 ndash highway 2 ndash main roads 3 ndash forest roads 4 ndash railways
5 ndash fish ponds 6 ndash forests 7 ndash closed Matylda mine 8 ndash built-up area
Samples of water (surface layer) were collected from the central and near-bank
parts of the SP MP LP and LoP ponds and from the UP only of its central part The
samples were taken monthly from April 2009 to March 2010 except of July 2009
(all ponds) and September 2009 (central parts of SP MP LP and LoP) The sampling
on dry spring of 2009 (April and May) was followed by wet early summer with rainfalls
in June exceeding a multi-year average by 150 The following August September and
October were warmer and dryer than average (rainfalls of 50ndash75 of norm) Soon after
the sampling in October rains and snowfall of about 60 mm raised water level both in
ponds and in their tributaries Sampling in November represented wet period with low
temperatures reducing evaporation Winter started at the end of December and sampling
in January was preceded by monthly period of frosts and accretion of ice cover to the
thickness of 10ndash15 cm Sampling was finished at the end of March after rapid snow
melting preceded by over one month of temperatures fluctuated about 0 degC A perma-
nent ice cover lasted until the end of March In the collected samples the following
124 E SZAREK-GWIAZDA D CISZEWSKI
parameters were determined pH conductivity dissolved oxygen anions (Clndash SO4
2ndash
HCO3ndash NO3
ndash) and cations (Na
+ K
+ Ca
2+ Mg
2+ NH4
+) BOD5 organic matter (LOI) and
concentrations of heavy metals (Cd Pb Zn Mn and Fe)
Physicochemical analysis Conductivity and pH were determined using WTW
(Multi 340 and SET 2) apparatus whereas dissolved oxygen and BOD5 by the Winkler
method In order to analyze the content of anions and cations (heavy metals as well)
water samples were filtered through 045 μm pore-sized syringe filters into a polyeth-
ylene container The contents of inorganic ions (Clndash SO4
2ndash HCO3
ndash NO3
ndash Na
+ K
+ Ca
2+
Mg2+
NH4+) were determined within 48 h using ion chromatography (DIONEX ICS
1000 and IC DX 320) For the metal analysis samples of water were acidified to pH lt 2
with ultrapure HNO3 The concentrations of Zn Cd Pb Fe and Mn were measured with
an inductively coupled plasma mass spectrometer (Perkin Elmer ELAN 6100) The or-
ganic matter was determined as losses on ignition (LOI) at 550 degC
The differences in the heavy metal concentrations in water between the studied
ponds were analyzed using the KruskalndashWallis test while those within one pond be-
tween its central and coastal parts by the Wilcoxon test The relationships between the
concentrations of heavy metals and the values of physicochemical parameters were de-
termined by the Spearman correlation
3 RESULTS
31 PHYSICOCHEMICAL PARAMETERS OF WATER
The values of physicochemical parameters in the studied ponds (median range) are
given in Table 1 The water of SP MP LP and LoP had pH of 70ndash97 while pH in UP
varied in the range of 49ndash76 During the most of the year the water of UP had acidic
reaction pH was significantly lower in UP than in MP and LP (Table 2) In all ponds
pH was usually higher in spring and summer and then decreased reaching the lowest
values in winter months (JanuaryndashMarch) (Fig 2)
The waters of SP MP LP and LoP were usually well oxygenated (gt8 mg O2middotdmndash3
)
while that of UP weakly oxygenated (lt4 mg O2middotdmndash3
) However a decrease in the amount
of dissolved oxygen below 4 mg O2middotdmndash3
appeared also periodically in the waters of SP and
LP in the summer autumn and winter months (Fig 2) The content of dissolved oxygen was
significantly lower in the water of UP than that of other ponds (Table 2)
The amounts of anions and cations varied among the studied ponds (Table 1) The
median values of conductivity Clndash SO4
2ndash HCO3
ndash Ca
2+ and Na
+ were the highest in the
water of SP (the first of the cascade of ponds directly supplied with waters from the
Matylda stream) while that of Mg2+
occurred in LP (the last of the cascade) The lowest
Heavy metal concentrations in waters affected by the former lead and zinc mine 125
median contents of major anions and cations (with the exception of K+) were found in
the water of UP (Table 1) Low values of studied anions and cations were also found in
LoP (supplied both with waters from the cascade of ponds and from the relatively un-
polluted tributary) Occasionally drastic increase in the contents of major anions and
cations appeared in the pond waters (UP in May and September in the central and near-
bank parts of SP in April and May Fig 3) which were not accompanied by high con-
centrations of heavy metals
The values of BOD5 (the content of easily degradable organic matter) varied in the
range 03ndash82 mg O2middotdmndash3
and the amount of LOI in the range 15ndash262 mgmiddotdmndash3
(Table 1)
The values of BOD5 and contents of LOI were similar in the studied ponds and increased
in different months Moreover the amount of nitrates was lower during growing season
and higher in autumn and winter months
T a b l e 1
Median (M) and range (R) values of physicochemical parameters and concentrations
of heavy metals in waters of the ponds situated in the Matylda catchment
Parameter UP SP MP LP LoP
M R M R M R M R M R
pH 63 49ndash76 75 70ndash85 79 70ndash89 83 70ndash97 74 70ndash86
Conductivity
microS middotcmndash1 2155
1100
ndash11250 4810
2590
ndash6360 4320
2450
ndash4900 4340
1400
ndash4880 3730 2570ndash4290
Dissolved O2
mgmiddotdmndash3 38 05ndash54 86 16ndash120 93 58ndash106 95 19ndash117 91 46ndash115
Clndash mgmiddotdmndash3 190 130ndash438 272 135ndash374 235 167ndash329 245 96ndash314 208 118ndash258
HCO3ndash mgmiddotdmndash3 481 93ndash4452 1519 591ndash2612 1342 694ndash2021 1298 418ndash1623 1252 636ndash1921
SO42ndash mgmiddotdmndash3 475 279ndash2301 802 461ndash1366 775 388ndash1114 753 207ndash987 486 256ndash753
Na+ mgmiddotdmndash3 85 28ndash290 138 90ndash197 123 69ndash170 125 42ndash161 108 69ndash132
K+ mgmiddotdmndash3 27 17ndash108 32 20ndash63 30 11ndash39 28 08ndash45 24 17ndash32
Ca2+ mgmiddotdmndash3 232 121ndash1523 602 305ndash868 523 274ndash664 520 163ndash645 451 315ndash542
Mg2+ mgmiddotdmndash3 50 22ndash428 135 64ndash239 119 49ndash160 138 30ndash150 106 64ndash123
NO3ndash mgmiddotdmndash3 063 005ndash285 215 003ndash1862 199 002ndash1010 076 002ndash1832 065 002ndash2228
NH4+ mgmiddotdmndash3 022 003ndash461 009 002ndash090 008 002ndash038 008 001ndash049 013 003ndash021
BOD5 mgmiddotdmndash3 20 03ndash34 29 03ndash64 32 10ndash82 19 03ndash58 21 05ndash53
LOI mgmiddotdmndash3 1110 680ndash1550 1210 520ndash1950 1170 610ndash2620 1240 150ndash1910 1110 680ndash1550
Cd gmiddotdmndash3 29 003ndash580 09 002ndash448 02 002ndash260 006 002ndash116 03 002ndash191
Pb gmiddotdmndash3 84 13ndash757 108 24ndash1473 46 16ndash180 55 11ndash1060 56 16ndash107
Zn gmiddotdmndash3 4836 646ndash8003 3444 137ndash7908 611 104ndash5615 258 26ndash2913 688 71ndash2894
Mn gmiddotdmndash3 1204 947ndash2878 853 134ndash9871 269 48ndash1906 197 37ndash878 1068 107ndash2935
Fe gmiddotdmndash3 8059 1644ndash25328 1715 20ndash11246 961 498ndash2975 598 13ndash11001 2513 670ndash6390
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower
pond LOI ndash loss of ignition
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 123
and supplied both with the waters from the cascade of ponds and relatively unpolluted
tributary The depth of the ponds reaches 2 m During the pond operation a part of
sediments was removed from the UP and LoP ponds whereas in the LP sediments were
shifted with a bulldozer toward the southeast banks of the pond Sediments of the MP
and SP ponds were intact
Fig 1 Locations of the research area and sampling points a) dykes and roads b) dykes
c) sampling points UP ndash upper pond SP ndash small pond MP ndash middle pond LP ndash large pond
LoP ndash lower pond 1 ndash highway 2 ndash main roads 3 ndash forest roads 4 ndash railways
5 ndash fish ponds 6 ndash forests 7 ndash closed Matylda mine 8 ndash built-up area
Samples of water (surface layer) were collected from the central and near-bank
parts of the SP MP LP and LoP ponds and from the UP only of its central part The
samples were taken monthly from April 2009 to March 2010 except of July 2009
(all ponds) and September 2009 (central parts of SP MP LP and LoP) The sampling
on dry spring of 2009 (April and May) was followed by wet early summer with rainfalls
in June exceeding a multi-year average by 150 The following August September and
October were warmer and dryer than average (rainfalls of 50ndash75 of norm) Soon after
the sampling in October rains and snowfall of about 60 mm raised water level both in
ponds and in their tributaries Sampling in November represented wet period with low
temperatures reducing evaporation Winter started at the end of December and sampling
in January was preceded by monthly period of frosts and accretion of ice cover to the
thickness of 10ndash15 cm Sampling was finished at the end of March after rapid snow
melting preceded by over one month of temperatures fluctuated about 0 degC A perma-
nent ice cover lasted until the end of March In the collected samples the following
124 E SZAREK-GWIAZDA D CISZEWSKI
parameters were determined pH conductivity dissolved oxygen anions (Clndash SO4
2ndash
HCO3ndash NO3
ndash) and cations (Na
+ K
+ Ca
2+ Mg
2+ NH4
+) BOD5 organic matter (LOI) and
concentrations of heavy metals (Cd Pb Zn Mn and Fe)
Physicochemical analysis Conductivity and pH were determined using WTW
(Multi 340 and SET 2) apparatus whereas dissolved oxygen and BOD5 by the Winkler
method In order to analyze the content of anions and cations (heavy metals as well)
water samples were filtered through 045 μm pore-sized syringe filters into a polyeth-
ylene container The contents of inorganic ions (Clndash SO4
2ndash HCO3
ndash NO3
ndash Na
+ K
+ Ca
2+
Mg2+
NH4+) were determined within 48 h using ion chromatography (DIONEX ICS
1000 and IC DX 320) For the metal analysis samples of water were acidified to pH lt 2
with ultrapure HNO3 The concentrations of Zn Cd Pb Fe and Mn were measured with
an inductively coupled plasma mass spectrometer (Perkin Elmer ELAN 6100) The or-
ganic matter was determined as losses on ignition (LOI) at 550 degC
The differences in the heavy metal concentrations in water between the studied
ponds were analyzed using the KruskalndashWallis test while those within one pond be-
tween its central and coastal parts by the Wilcoxon test The relationships between the
concentrations of heavy metals and the values of physicochemical parameters were de-
termined by the Spearman correlation
3 RESULTS
31 PHYSICOCHEMICAL PARAMETERS OF WATER
The values of physicochemical parameters in the studied ponds (median range) are
given in Table 1 The water of SP MP LP and LoP had pH of 70ndash97 while pH in UP
varied in the range of 49ndash76 During the most of the year the water of UP had acidic
reaction pH was significantly lower in UP than in MP and LP (Table 2) In all ponds
pH was usually higher in spring and summer and then decreased reaching the lowest
values in winter months (JanuaryndashMarch) (Fig 2)
The waters of SP MP LP and LoP were usually well oxygenated (gt8 mg O2middotdmndash3
)
while that of UP weakly oxygenated (lt4 mg O2middotdmndash3
) However a decrease in the amount
of dissolved oxygen below 4 mg O2middotdmndash3
appeared also periodically in the waters of SP and
LP in the summer autumn and winter months (Fig 2) The content of dissolved oxygen was
significantly lower in the water of UP than that of other ponds (Table 2)
The amounts of anions and cations varied among the studied ponds (Table 1) The
median values of conductivity Clndash SO4
2ndash HCO3
ndash Ca
2+ and Na
+ were the highest in the
water of SP (the first of the cascade of ponds directly supplied with waters from the
Matylda stream) while that of Mg2+
occurred in LP (the last of the cascade) The lowest
Heavy metal concentrations in waters affected by the former lead and zinc mine 125
median contents of major anions and cations (with the exception of K+) were found in
the water of UP (Table 1) Low values of studied anions and cations were also found in
LoP (supplied both with waters from the cascade of ponds and from the relatively un-
polluted tributary) Occasionally drastic increase in the contents of major anions and
cations appeared in the pond waters (UP in May and September in the central and near-
bank parts of SP in April and May Fig 3) which were not accompanied by high con-
centrations of heavy metals
The values of BOD5 (the content of easily degradable organic matter) varied in the
range 03ndash82 mg O2middotdmndash3
and the amount of LOI in the range 15ndash262 mgmiddotdmndash3
(Table 1)
The values of BOD5 and contents of LOI were similar in the studied ponds and increased
in different months Moreover the amount of nitrates was lower during growing season
and higher in autumn and winter months
T a b l e 1
Median (M) and range (R) values of physicochemical parameters and concentrations
of heavy metals in waters of the ponds situated in the Matylda catchment
Parameter UP SP MP LP LoP
M R M R M R M R M R
pH 63 49ndash76 75 70ndash85 79 70ndash89 83 70ndash97 74 70ndash86
Conductivity
microS middotcmndash1 2155
1100
ndash11250 4810
2590
ndash6360 4320
2450
ndash4900 4340
1400
ndash4880 3730 2570ndash4290
Dissolved O2
mgmiddotdmndash3 38 05ndash54 86 16ndash120 93 58ndash106 95 19ndash117 91 46ndash115
Clndash mgmiddotdmndash3 190 130ndash438 272 135ndash374 235 167ndash329 245 96ndash314 208 118ndash258
HCO3ndash mgmiddotdmndash3 481 93ndash4452 1519 591ndash2612 1342 694ndash2021 1298 418ndash1623 1252 636ndash1921
SO42ndash mgmiddotdmndash3 475 279ndash2301 802 461ndash1366 775 388ndash1114 753 207ndash987 486 256ndash753
Na+ mgmiddotdmndash3 85 28ndash290 138 90ndash197 123 69ndash170 125 42ndash161 108 69ndash132
K+ mgmiddotdmndash3 27 17ndash108 32 20ndash63 30 11ndash39 28 08ndash45 24 17ndash32
Ca2+ mgmiddotdmndash3 232 121ndash1523 602 305ndash868 523 274ndash664 520 163ndash645 451 315ndash542
Mg2+ mgmiddotdmndash3 50 22ndash428 135 64ndash239 119 49ndash160 138 30ndash150 106 64ndash123
NO3ndash mgmiddotdmndash3 063 005ndash285 215 003ndash1862 199 002ndash1010 076 002ndash1832 065 002ndash2228
NH4+ mgmiddotdmndash3 022 003ndash461 009 002ndash090 008 002ndash038 008 001ndash049 013 003ndash021
BOD5 mgmiddotdmndash3 20 03ndash34 29 03ndash64 32 10ndash82 19 03ndash58 21 05ndash53
LOI mgmiddotdmndash3 1110 680ndash1550 1210 520ndash1950 1170 610ndash2620 1240 150ndash1910 1110 680ndash1550
Cd gmiddotdmndash3 29 003ndash580 09 002ndash448 02 002ndash260 006 002ndash116 03 002ndash191
Pb gmiddotdmndash3 84 13ndash757 108 24ndash1473 46 16ndash180 55 11ndash1060 56 16ndash107
Zn gmiddotdmndash3 4836 646ndash8003 3444 137ndash7908 611 104ndash5615 258 26ndash2913 688 71ndash2894
Mn gmiddotdmndash3 1204 947ndash2878 853 134ndash9871 269 48ndash1906 197 37ndash878 1068 107ndash2935
Fe gmiddotdmndash3 8059 1644ndash25328 1715 20ndash11246 961 498ndash2975 598 13ndash11001 2513 670ndash6390
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower
pond LOI ndash loss of ignition
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
124 E SZAREK-GWIAZDA D CISZEWSKI
parameters were determined pH conductivity dissolved oxygen anions (Clndash SO4
2ndash
HCO3ndash NO3
ndash) and cations (Na
+ K
+ Ca
2+ Mg
2+ NH4
+) BOD5 organic matter (LOI) and
concentrations of heavy metals (Cd Pb Zn Mn and Fe)
Physicochemical analysis Conductivity and pH were determined using WTW
(Multi 340 and SET 2) apparatus whereas dissolved oxygen and BOD5 by the Winkler
method In order to analyze the content of anions and cations (heavy metals as well)
water samples were filtered through 045 μm pore-sized syringe filters into a polyeth-
ylene container The contents of inorganic ions (Clndash SO4
2ndash HCO3
ndash NO3
ndash Na
+ K
+ Ca
2+
Mg2+
NH4+) were determined within 48 h using ion chromatography (DIONEX ICS
1000 and IC DX 320) For the metal analysis samples of water were acidified to pH lt 2
with ultrapure HNO3 The concentrations of Zn Cd Pb Fe and Mn were measured with
an inductively coupled plasma mass spectrometer (Perkin Elmer ELAN 6100) The or-
ganic matter was determined as losses on ignition (LOI) at 550 degC
The differences in the heavy metal concentrations in water between the studied
ponds were analyzed using the KruskalndashWallis test while those within one pond be-
tween its central and coastal parts by the Wilcoxon test The relationships between the
concentrations of heavy metals and the values of physicochemical parameters were de-
termined by the Spearman correlation
3 RESULTS
31 PHYSICOCHEMICAL PARAMETERS OF WATER
The values of physicochemical parameters in the studied ponds (median range) are
given in Table 1 The water of SP MP LP and LoP had pH of 70ndash97 while pH in UP
varied in the range of 49ndash76 During the most of the year the water of UP had acidic
reaction pH was significantly lower in UP than in MP and LP (Table 2) In all ponds
pH was usually higher in spring and summer and then decreased reaching the lowest
values in winter months (JanuaryndashMarch) (Fig 2)
The waters of SP MP LP and LoP were usually well oxygenated (gt8 mg O2middotdmndash3
)
while that of UP weakly oxygenated (lt4 mg O2middotdmndash3
) However a decrease in the amount
of dissolved oxygen below 4 mg O2middotdmndash3
appeared also periodically in the waters of SP and
LP in the summer autumn and winter months (Fig 2) The content of dissolved oxygen was
significantly lower in the water of UP than that of other ponds (Table 2)
The amounts of anions and cations varied among the studied ponds (Table 1) The
median values of conductivity Clndash SO4
2ndash HCO3
ndash Ca
2+ and Na
+ were the highest in the
water of SP (the first of the cascade of ponds directly supplied with waters from the
Matylda stream) while that of Mg2+
occurred in LP (the last of the cascade) The lowest
Heavy metal concentrations in waters affected by the former lead and zinc mine 125
median contents of major anions and cations (with the exception of K+) were found in
the water of UP (Table 1) Low values of studied anions and cations were also found in
LoP (supplied both with waters from the cascade of ponds and from the relatively un-
polluted tributary) Occasionally drastic increase in the contents of major anions and
cations appeared in the pond waters (UP in May and September in the central and near-
bank parts of SP in April and May Fig 3) which were not accompanied by high con-
centrations of heavy metals
The values of BOD5 (the content of easily degradable organic matter) varied in the
range 03ndash82 mg O2middotdmndash3
and the amount of LOI in the range 15ndash262 mgmiddotdmndash3
(Table 1)
The values of BOD5 and contents of LOI were similar in the studied ponds and increased
in different months Moreover the amount of nitrates was lower during growing season
and higher in autumn and winter months
T a b l e 1
Median (M) and range (R) values of physicochemical parameters and concentrations
of heavy metals in waters of the ponds situated in the Matylda catchment
Parameter UP SP MP LP LoP
M R M R M R M R M R
pH 63 49ndash76 75 70ndash85 79 70ndash89 83 70ndash97 74 70ndash86
Conductivity
microS middotcmndash1 2155
1100
ndash11250 4810
2590
ndash6360 4320
2450
ndash4900 4340
1400
ndash4880 3730 2570ndash4290
Dissolved O2
mgmiddotdmndash3 38 05ndash54 86 16ndash120 93 58ndash106 95 19ndash117 91 46ndash115
Clndash mgmiddotdmndash3 190 130ndash438 272 135ndash374 235 167ndash329 245 96ndash314 208 118ndash258
HCO3ndash mgmiddotdmndash3 481 93ndash4452 1519 591ndash2612 1342 694ndash2021 1298 418ndash1623 1252 636ndash1921
SO42ndash mgmiddotdmndash3 475 279ndash2301 802 461ndash1366 775 388ndash1114 753 207ndash987 486 256ndash753
Na+ mgmiddotdmndash3 85 28ndash290 138 90ndash197 123 69ndash170 125 42ndash161 108 69ndash132
K+ mgmiddotdmndash3 27 17ndash108 32 20ndash63 30 11ndash39 28 08ndash45 24 17ndash32
Ca2+ mgmiddotdmndash3 232 121ndash1523 602 305ndash868 523 274ndash664 520 163ndash645 451 315ndash542
Mg2+ mgmiddotdmndash3 50 22ndash428 135 64ndash239 119 49ndash160 138 30ndash150 106 64ndash123
NO3ndash mgmiddotdmndash3 063 005ndash285 215 003ndash1862 199 002ndash1010 076 002ndash1832 065 002ndash2228
NH4+ mgmiddotdmndash3 022 003ndash461 009 002ndash090 008 002ndash038 008 001ndash049 013 003ndash021
BOD5 mgmiddotdmndash3 20 03ndash34 29 03ndash64 32 10ndash82 19 03ndash58 21 05ndash53
LOI mgmiddotdmndash3 1110 680ndash1550 1210 520ndash1950 1170 610ndash2620 1240 150ndash1910 1110 680ndash1550
Cd gmiddotdmndash3 29 003ndash580 09 002ndash448 02 002ndash260 006 002ndash116 03 002ndash191
Pb gmiddotdmndash3 84 13ndash757 108 24ndash1473 46 16ndash180 55 11ndash1060 56 16ndash107
Zn gmiddotdmndash3 4836 646ndash8003 3444 137ndash7908 611 104ndash5615 258 26ndash2913 688 71ndash2894
Mn gmiddotdmndash3 1204 947ndash2878 853 134ndash9871 269 48ndash1906 197 37ndash878 1068 107ndash2935
Fe gmiddotdmndash3 8059 1644ndash25328 1715 20ndash11246 961 498ndash2975 598 13ndash11001 2513 670ndash6390
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower
pond LOI ndash loss of ignition
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 125
median contents of major anions and cations (with the exception of K+) were found in
the water of UP (Table 1) Low values of studied anions and cations were also found in
LoP (supplied both with waters from the cascade of ponds and from the relatively un-
polluted tributary) Occasionally drastic increase in the contents of major anions and
cations appeared in the pond waters (UP in May and September in the central and near-
bank parts of SP in April and May Fig 3) which were not accompanied by high con-
centrations of heavy metals
The values of BOD5 (the content of easily degradable organic matter) varied in the
range 03ndash82 mg O2middotdmndash3
and the amount of LOI in the range 15ndash262 mgmiddotdmndash3
(Table 1)
The values of BOD5 and contents of LOI were similar in the studied ponds and increased
in different months Moreover the amount of nitrates was lower during growing season
and higher in autumn and winter months
T a b l e 1
Median (M) and range (R) values of physicochemical parameters and concentrations
of heavy metals in waters of the ponds situated in the Matylda catchment
Parameter UP SP MP LP LoP
M R M R M R M R M R
pH 63 49ndash76 75 70ndash85 79 70ndash89 83 70ndash97 74 70ndash86
Conductivity
microS middotcmndash1 2155
1100
ndash11250 4810
2590
ndash6360 4320
2450
ndash4900 4340
1400
ndash4880 3730 2570ndash4290
Dissolved O2
mgmiddotdmndash3 38 05ndash54 86 16ndash120 93 58ndash106 95 19ndash117 91 46ndash115
Clndash mgmiddotdmndash3 190 130ndash438 272 135ndash374 235 167ndash329 245 96ndash314 208 118ndash258
HCO3ndash mgmiddotdmndash3 481 93ndash4452 1519 591ndash2612 1342 694ndash2021 1298 418ndash1623 1252 636ndash1921
SO42ndash mgmiddotdmndash3 475 279ndash2301 802 461ndash1366 775 388ndash1114 753 207ndash987 486 256ndash753
Na+ mgmiddotdmndash3 85 28ndash290 138 90ndash197 123 69ndash170 125 42ndash161 108 69ndash132
K+ mgmiddotdmndash3 27 17ndash108 32 20ndash63 30 11ndash39 28 08ndash45 24 17ndash32
Ca2+ mgmiddotdmndash3 232 121ndash1523 602 305ndash868 523 274ndash664 520 163ndash645 451 315ndash542
Mg2+ mgmiddotdmndash3 50 22ndash428 135 64ndash239 119 49ndash160 138 30ndash150 106 64ndash123
NO3ndash mgmiddotdmndash3 063 005ndash285 215 003ndash1862 199 002ndash1010 076 002ndash1832 065 002ndash2228
NH4+ mgmiddotdmndash3 022 003ndash461 009 002ndash090 008 002ndash038 008 001ndash049 013 003ndash021
BOD5 mgmiddotdmndash3 20 03ndash34 29 03ndash64 32 10ndash82 19 03ndash58 21 05ndash53
LOI mgmiddotdmndash3 1110 680ndash1550 1210 520ndash1950 1170 610ndash2620 1240 150ndash1910 1110 680ndash1550
Cd gmiddotdmndash3 29 003ndash580 09 002ndash448 02 002ndash260 006 002ndash116 03 002ndash191
Pb gmiddotdmndash3 84 13ndash757 108 24ndash1473 46 16ndash180 55 11ndash1060 56 16ndash107
Zn gmiddotdmndash3 4836 646ndash8003 3444 137ndash7908 611 104ndash5615 258 26ndash2913 688 71ndash2894
Mn gmiddotdmndash3 1204 947ndash2878 853 134ndash9871 269 48ndash1906 197 37ndash878 1068 107ndash2935
Fe gmiddotdmndash3 8059 1644ndash25328 1715 20ndash11246 961 498ndash2975 598 13ndash11001 2513 670ndash6390
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower
pond LOI ndash loss of ignition
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
126 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 2
The significance of differences in the values of physicochemical
parameters and heavy metal concentrations in the waters
of the studied ponds in the Matylda catchmenta
Parameter The value of statistics Ponds
Dissolved O2 H5103 = 2598 p = 00001 UP lt SP MP LP LoP
pH H9104 = 2455 p = 00002 UP lt MP LP
Conductivity H9104 = 3441 p = 00000 SP gt LoP UP
Clndash H5104 = 1558 p = 00082 SP gt LoP
SO42ndash H5104 = 3174 p = 00000 SP MP LP gt LoP
Na+ H5104 = 2267 p = 00004 SP gt UP LoP
K+ H5104 = 2483 p = 00002 SP MP gt LoP
Ca2+ H5104 = 3416 p = 00000 SP gt UP LoP
Mg2+ H5104 = 3106 p = 00000 SP LP gt LoP
Cd H5103 = 1620 p = 00063 UP gt LP
Pb H5103 = 2719 p = 00001 SP gt LP LoP
Zn H5103 = 1738 p = 00038 UP gt LP
Mn H5103 = 5037 p = 00000
LoP gt MP LP
SP UP gt LP
UP gt MP
Fe H5103 = 4997 p = 00000
UP gt MP LP
SP gt LP
LoP gt MP LP a The KruskalndashWallis test the value of p for multiple comparisons Only
significant differences are given UP ndash upper pond cascade of ponds
SP ndash small pond MP ndash middle pond LP ndash large pond LoP ndash lower pond
p ndash significance level
The concentration ranges of heavy metals in the pond waters (microgmiddotdmndash3
) were
Cd 002ndash580 Pb 11ndash1473 Zn 26ndash8003 Mn 37ndash9870 and Fe 13ndash2533 (Table 1
Figs 2 and 4) There were marked differences among the studied ponds in them
Higher median concentrations of Cd Pb Zn and Fe were found in the waters of UP
and SP located closer to the discharge point of mine waters than in the remaining
ponds (Table 1) The differences of median concentrations of the investigated metals
between UP and the remaining ponds were considerable for Cd (2ndash48 times) Fe
(3ndash13 times) Pb (15ndash4 times) and Zn (4ndash18 times) A decrease in the median heavy
metal concentrations down the cascade of ponds ndash SP MP and LP ndash was larger in the
central part of ponds than at their banks Differences in median values between SP
and LP for Zn equal 11 times for Cd ndash 7 times while for Pb Mn and Fe 22ndash32 times
Differences in concentrations of Pb Mn and Fe between SP and LP as well as of Pb
between SP and LoP were statistically significant (Table 2) The concentrations of Mn
and Fe in the waters of MP and LP were significantly lower than of UP and LoP
(Table 2)
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 127
Fig 2 Dissolved oxygen content pH and the concentrations of Mn and Fe
in the surface water of the studied ponds in the Matylda catchment
The concentrations of heavy metals and values of some parameters also showed
marked differences among the studied parts of the ponds Significantly higher concen-
trations of Mn (Z = 199 p = 0047) Cu (Z = 237 p = 0018) and Na+ (Z = 199 p =
0047) in SP Mn (Z = 260 p = 0009) Fe (Z = 260 p = 0009) Zn (Z = 229
p = 0022) and NO3ndash (Z = 199 p = 0047) in LoP while lower pH (Z = 255 p = 0011)
and SO42ndash
content (Z = 260 p = 0009) in MP were found in the coastal in comparison
to the central parts of the ponds
32 HEAVY METALS IN WATER
During most of the year concentrations of heavy metals in pond waters were rela-
tively low but periodically their considerable increases were found (Figs 2 and 4) High
concentrations of heavy metals in UP occurred in various months while in the cascade
of ponds and LoP mainly in winter months until March and additionally in SP in late
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
128 E SZAREK-GWIAZDA D CISZEWSKI
summer and LoP in spring and summer In winter months they usually occurred in cen-
tral andor near-bank parts while in late summer and early autumn only in the near-
bank parts In general high concentrations of heavy metals in the water of cascade ponds
and LoP were found at neutral reaction (Figs 2 and 4) As was mentioned above water
in UP had slightly acidic or neutral reaction during most of the year
Fig 3 Conductivities and the content of major ions in the surface water
of the Upper Pond in the Matylda catchment
High concentrations of heavy metals were found at low content of dissolved oxygen
(lt2 mg O2middotdmndash3
) and increased content of NH4+ (038ndash090 mgmiddotdm
ndash3) In such condi-
tions maximum or high concentrations of Pb and Fe appeared in August of Mn Fe
Cd and Zn in November in UP those of Mn and Fe in SP in September whereas those
of Mn and Pb in February in LP (Figs 2 and 4)
High concentrations of heavy metals in the pond waters were also related to the
high content of organic matter (expressed as BOD5 43ndash82 mg O2middotdmndash3
and LOI
145ndash262 mgmiddotdmndash3
) and occasionally to NH4+ (04ndash09 mgmiddotdm
ndash3) and some other ions
(Clndash 304ndash32 9 mgmiddotdm
ndash3 Na
+ 15ndash17 mgmiddotdm
ndash3) In the water of UP maximum concen-
trations of Cd Zn and the values of BOD5 were found in January high contents of Cd
Zn and the values of BOD5 in June In the near-bank part of SP the high concentrations
of Cd and Pb and LOI were found in January Cd Zn Mn and the values of BOD5 in
February Cd Zn and LOI in well oxygenated water (gt8 mg O2middotdmndash3
) in March while
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 129
those of Cd Pb Zn Fe and the value of BOD5 in August In both parts of MP high concen-
trations of Cd Pb and Zn LOI Clndash and Na
+ ions and the values BOD5 (only central part)
were found in January while of Cd Pb Zn Mn Fe N-NH4 Clndash and Na
+ ions in February
In the coastal part of LP the maximum concentration of Fe and elevated values of BOD5
were found in December In LoP high contents of Cd Zn and LOI occurred in both parts of
the pond and of NH4+ in its central part from January to March while Fe LOI SO4
2ndash in both
parts and Pb in the central one in December Additionally maximum content of Pb high
values of LOI and of all studied ions accompanied by a minimum content of dissolved ox-
ygen (46 mg O2middotdmndash3
) were found in LoP in September
Fig 4 The concentrations of Cd Pb and Zn in the surface water
of the studied ponds in the Matylda catchment
Moreover a lack of relationship between high metal concentrations and the values
of studied parameters was found High concentrations of Cd Zn and Fe accompanied
by minimum concentrations of major anions and cations (SO42ndash
HCO3ndash Cl
ndash Na
+ K
+
Ca2+
Mg2+
) and low contents of organic matter (BOD5 LOI) were found in the central
part of LP in March High concentrations of Mn in LoP did not also show any clear
relationships with other parameters
During the whole studied period metal concentrations in pond water depended
(negative correlations) on pH (Cd in UP Cd Zn and Fe in SP Cd Pb Zn Mn and Fe
in MP Cd Zn and Mn in LP Cd and Zn in LoP) and on the amount of dissolved oxygen
(Mn in UP and SP Mn and Fe in LP) (Table 3)
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
130 E SZAREK-GWIAZDA D CISZEWSKI
T a b l e 3
The relationship between concentrations of heavy metals and values
of physicochemical parameters in water of the studied ponds in the Matylda catchment
Parameter
Pond Pond
UP SP MP LP LoP UP SP MP LP LoP
N N
10 21 21 21 21 10 21 21 21 21
Cd Fe
pH ndash072 ndash062 ndash081 ndash046 ndash076 ns ndash044 ndash078 ns ns
Dissolved O2 ndash ndash044 ndash078 ns ns ns
Conductivity ndash065 ndash068 ns ns ndash069
SO42ndash ns ndash045 ns ndash044 ns ns ndash046 ns ns ns
HCO3ndash ndash092 ndash075 ndash054 ns ndash065 ns ns ndash056 ns ns
Na+ ndash064 ndash047 ns ns ndash049 ns ns ns ns ndash051
K+ ns ndash084 ns ns ndash057
Ca2+ ndash066 ndash058 ns ns ndash066 ns ns ns ns ndash046
Mg2+ ndash071 ndash078 ndash048 ndash051 ndash066 ns ns ndash056 ns ns
NO3ndash ns 059 065 063 068 ns ns 060 ns 051
NH4+ ns ns 075 ns ns ns ns 056 ns ns
BOD5 ns ns ndash056 ns ndash056
LOI ns 048 048 ns ns 065 ns ns ns ns
Pb Mn
pH ns ns ndash079 ns ns ns ns ndash076 ndash046 ns
Dissolved O2 ndash ndash074 ndash060 ns ndash060 ns
SO42ndash ndash066 ns ns ns ns
HCO3ndash ns ns ndash055 ns ns ns ns ndash049 ns ns
Mg2+ ns ns ndash048 ns ns ns ns ndash055 ns ns
NO3ndash ns 045 069 ns ns ns ns 061 ns ns
NH4+ ns ns 060 ns ns ns ns 069 067 054
BOD5 ns ns ndash055 ns ns ndash
Zn Interactions between metals
pH ns ndash049 ndash086 ndash051 ndash086 CdndashPb ns ns 094 070 ns
Conductivity ndash064 ns ns ns ndash071 CdndashZn 089 080 092 075 094
Clndash ndash066 ns ns ns ns PbndashZn ns 044 092 ns ns
SO42ndash ns ns ns ndash045 ns MnndashFe ns 046 085 ns ns
HCO3ndash ndash073 ndash049 ndash060 ns ndash075 MnndashCd ns ns 083 ns ns
Na+ ndash072 ns ns ns ndash050 MnndashPb ns 044 078 ns ns
K+ ns ndash059 ns ns ndash059 MnndashZn ns ns 080 ns ns
Ca2+ ns ns ns ns ndash066 FendashCd ns ns 086 050 ns
Mg2+ ns ndash059 ndash052 ndash045 ndash065 FendashPb ns ns 087 045 ns
NO3ndash ns 055 079 059 074 FendashZn ns 055 089 051 049
NH4+ ndash066 ns 065 ns ns ndash
BOD5 ns ns ndash055 ns ndash052 ndash
UP ndash upper pond cascade of ponds SP ndash small pond MP ndash middle pond LP ndash large
pond LoP ndash lower pond LOI ndash loss of ignition
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 131
The positive correlations were found between the metal concentrations and the con-
tent of nitrates (Cd Pb and Zn in UP Mn Fe Cd Pb and Zn in MP Cd and Zn in LP
Cd Zn and Fe in LoP) values of NH4+ (Mn Fe Cd Pb and Zn in MP Mn in LP and
LoP) There were also positive correlations between the pairs of metals (CdndashZn in UP
FendashMn CdndashZn PbndashZn MnndashPb FendashZn in SP) In general the heavy metal concentra-
tions in the studied ponds showed negative correlations with the content of anions ie
Cd Pb Zn Mn and Fe with SO42ndash
and HCO3ndash Zn with Cl
ndash (Table 3)
4 DISCUSSION
The characteristic feature of the chemical composition of water of the studied ponds
were the increased amounts of sulfates and hydrocarbonates in comparison to the natural
waters of southern Poland [13] It was associated with predominance of carbonates
bearing sulfidic Zn-Pb ores which outcrop in the Matylda catchment [14] Besides nat-
ural sources which affect chemical composition of the studied waters during a year also
pond and stream sediments as well as contaminated soils of the catchment and occa-
sional uncontrolled discharge of domestic effluents in the upper part of the catchment
[2] can periodically increase the contents of anions and cations in pond water It was
found [12] that after the mine closure in the 1970s densely forested floodplain of the
Matylda Stream dissected by the network of ditches became a source of irregular in-
crease of major ions (Ca Mg chlorides carbonates and nitrates) in groundwater The
increased contents of major ions and metals in SP filled with mine-originated deposits
of the thickness even up to 1 m suggests that the sediments were their considerable
source
The seasonal changes of decomposition of organic matter undoubtedly affect water
oxygenation The studied ponds (with the exception of UP) were well oxygenated dur-
ing the most of the year whereas weakly (lt2 mg O2middotdmndash3
) only periodically Hence
deduced changes in the sediment redox conditions may affect the concentrations of the
most sensitive elements (like Mn in SP LP LoP and LP Fe in SP) in the water of
studied ponds that is typical of varied aquatic ecosystems [15ndash18] Maximum or high
concentrations of metals in the pond waters under reducing conditions accompanied by
dissolved oxygen content in the range of 05ndash19 mg O2middotdmndash3
and slightly acidic and
neutral conditions indicate their possible release from the bottom sediments This has
been expected because the pond sediments are still heavily contaminated with Cd
(130ndash340 microgmiddotgndash1
) Zn (10 000ndash50 000 microgmiddotgndash1
) and Pb (4000ndash12 000 microgmiddotgndash1
) and the
amounts of these metals in reducible phase are large and varied in the range 50ndash80 on
average [2] It is well known that under reduced conditions metals bound to easily re-
ducible fraction may be released after decomposition of Fe and Mn oxides [19] Such
ldquointernal loadingrdquo the best observed in SP largely filled with organic deposits seems to
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
132 E SZAREK-GWIAZDA D CISZEWSKI
be a considerable source of the metals in the waters of the Matylda ponds This phe-
nomenon was also observed in other water bodies [20 13] Although the water contam-
ination caused by this process occurred occasionally mostly in winter (February) but
also in summer (August and September) and autumn (November) its magnitude evi-
denced by the increase in metal concentrations was quite large The positive correlations
between the concentrations of Mn and Fe and other heavy metals in waters of the studied
ponds indicate that they were subjected to redox driven remobilization processes The
obtained relationships suggest that sorption and dissolution of Fe compounds played an
important role in the migration of Zn in SP and MP Cd and Pb in MP while circulation
of Mn compounds could affect the migration of Pb in SP Cd Pb and Zn in MP what
was also observed in other water bodies [15 19]
The obtained results indicated that organic matter (expressed as BOD5 and LOI)
play an important role in the migration of heavy metals in the studied ponds It is known
that functional groups of humic substances which are a mixture of fulvic and humic
acids bind heavy metals (Cd Pb and Zn) and in this way modify metal bioavailability
their transport and content in water environment [21] In reservoirs characterized by
a high content of dissolved organic matter (DOM) the proportion of metals (Cd Pb
and Zn) bound in complexes with DOM can reach 60ndash98 In the Matylda catchment
large portion of metals probably entered ponds in the form of metal-humic complexes
leached from the swampy soils of the valley bottom the forested catchment or from the
bed of numerous ditches covered with the fallen and decaying leaves It is known that
leaching of recent photosynthate (leaf litter root exudates decaying fine roots) or mi-
crobiological decomposition processes of organic matter are the most important source
of DOC [22] Decomposition processes promote acidification of soil substrate increase
the content of humic substances reduce forms of mineral substances (such as metals
ammonia) and decrease of pH in draining water Appearance of high or maximum con-
tent of heavy metals organic matter (expressed as LOI BOD5) and NH4+ accompanied
by low pH in the water of the studied ponds especially in the near-bank shallows in
winter and periodically in summer may indicate these phenomena
The fluctuations of the contents of dissolved metals in pond waters were probably
influenced by seasonal pattern of plant growth and decay Thus lower metal concentra-
tions during vegetation period might also be related to some extent to metal uptake by
macrophytes and algae which developed in the studied ponds during the growing sea-
son [10] Many annual macrophytes release significant quantities of C N and P and
metals [23] to the surrounding water after decay Macrophytes especially submerged
species growing in the studied ponds contained increased metal (mainly Pb and Zn)
concentrations [4] therefore their senescence and decay may be an important source of
metals Additionally decomposition of the organic matter affects decrease of pH which
favors release of metals from the sediments The obtained results indicate that water pH
control to the large extent (negative correlations) concentrations of all heavy metals in
the ponds situated on the Matylda Stream what was also proved in many other water
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 133
bodies [17 18] Therefore the highest metal concentrations (especially Cd and Zn) were
usually observed in all ponds in winter months when pH was the lowest
The considerable fluctuations in metal concentrations in the studied ponds con-
trolled adaptation of planktonic communities to persistent heavy metal contamination
[10] In the cascade of ponds (SP-MP-LP) the species resistant to high concentration of
heavy metals and characteristic for waters contaminated with heavy metals like
Achnantes cryptocephala A minutissima Surirella ovata and Eunotia exigua were
noted [10] Both diatoms and green algae present in the investigated fishponds were
described as species tolerant to heavy metals and high pollution High concentrations of
Zn and Pb in dissolved form in the water of SP were reflected in their high contents in
shoots of Myriophyllum spicatum [4] The process of biosorption of some metals on the
surface of M spicatum may be very fast (about 20 min) and followed by their slow
accumulation and translocation to the biomass [24] Myriophyllum shows much higher
capacity to absorb heavy metals and lower tolerance against stress conditions than Cer-
atophyllum [25] Decline of Myriophyllum and continuous presence of Ceratophyllum
in SP in the whole vegetation season were probably caused by water pollution by the
metals [4] Therefore periodical appearance of high metal concentrations in the studied
ponds may have a detrimental effect on biota
The obtained results showed that the occurrence of high concentrations of heavy
metals in the Matylda ponds were affected by the distribution of contaminated sedi-
ments both within ponds and in the valley bottom and by periodically varied physical
and geochemical processes Pond waters were more perceptible in near-bank parts than
in the central ones (significant differences in the concentrations of Mn in SP Mn Fe
Zn and nitrates in LoP higher median concentrations of Cd (24 times) and Mn
(16 times) and maximum concentrations of Pb Mn and Fe) During most of the year
the concentrations of heavy metals in dissolved forms (except for Zn) were similar to
those found in slightly polluted rivers [26] Higher than average concentrations of heavy
metals reaching up to 85 μg Cdmiddotdmminus3
147 μg Pbmiddotdmminus3
8003 μg Znmiddotdmminus3
9871 μg
Mnmiddotdmminus3
and 25328 μg Femiddotdmminus3
occurred only on some sampling occasions and were
similar to those found in the Biała Przemsza River in this region contaminated by active
lead and zinc mines [27] and to other rivers in the industrial regions [28] The decrease
in the maximum concentrations of metals in pond waters (from UP to LP) might be
associated with differences in the contamination of pond sediments [2] and soils in the
catchment
5 CONCLUSIONS
During this study heavy metal (Cd Pb Zn Mn and Fe) concentrations in waters of
five fishponds (UP SP MP LP and LoP) located in the Matylda catchment in the Up-
per Silesian Industrial Region in southern Poland were analyzed All ponds for over
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
134 E SZAREK-GWIAZDA D CISZEWSKI
100 years utilized mine waters from the lead and zinc mine Matylda The chemical
composition of the pond waters (decreased amounts of sulfates and hydrocarbonates
in comparison to surface water of rivers in southern Poland) reflected the geochemical
background of the catchment eg Triasssic dolomites bearing sulfidic ZnndashPb ore de-
posits and Holocene fluvial sandy sediments filling most of the valley bottom The
pond waters were usually well oxygenated and decrease in dissolved oxygen content
(lt2 mg O2middotdmndash3
) due to organic matter decomposition was only periodically observed
During prevailing part of the year pond waters were characterized by low concen-
trations of most heavy metals in dissolved forms which were similar or slightly de-
creased if compared to those in moderately industrialized areas Higher or maximum
metal concentrations noted usually in winter and occasionally in summer and autumn
could be related to annual cycling of organic matter production and degradation within
each pond The largest dissolved metal maxima including Fe and Mn occurred in ponds
with the most contaminated sediments Lower metal concentrations during vegetation
period might be caused by metal uptake by algae and rise of pH during algae develop-
ment
High or maximum concentrations of heavy metals were induced mainly by ldquointernal
loadingrdquo eg remobilization of metals from contaminated mostly organic bottom sed-
iments [4] whereas external sources due to small amount and contamination of water
supplied from the Matylda Stream seem to be less important [2] Organic matter decom-
position in winter resulted in an increase in the reductive conditions enhanced by ice
cover and in the decrease of pH to about neutral promoting dissolution of Mn and Fe
compounds which may bound over 50 of heavy metal contents in bottom sediments
The highest metal concentrations at the end of summer and in early autumn (August
ndashNovember) may be additionally explained by dying and degradation of algae and sub-
merged macrophytes enhanced at the end of the vegetation season Influence of variable
redox conditions on geochemistry of Mn and Fe compounds is confirmed by the nega-
tive correlation of oxygen content with Mn and Fe in some ponds (SP LP LoP and LP)
whereas negative correlation of pH with heavy metal concentrations suggest influence
of this parameter on content of Cd and Zn in all ponds and content of Pb in MP Mn in
MP and LP and Fe in SP and MP
The organic matter originates also from fall and decay of leaves in the forested
catchment dissected by numerous ditches draining contaminated sandy deposits of val-
ley bottom and swampy areas in the middle reach of the Matylda Stream The process
was more intensive during winter when frozen subsurface favored washing during melt-
ing and rainy periods which alternated with weak frost and snowing as well after longer
raining periods of summer Metals could be washed out and transported in the form of
metal-humus complexes This phenomenon is indicated by co-occurrence of maximum
or high contents of heavy metals organic matter (expressed as BOD5 and LOI) and
N-NH4 and slightly acidic or neutral pH in the pond waters especially in the near-bank
parts in winter and summer months
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
Heavy metal concentrations in waters affected by the former lead and zinc mine 135
ACKNOWLEDGEMENT
The study was financed by the Ministry of Science and Higher Education (grant No N 305 232 735)
and partly by the Institute of Nature Conservation Polish Academy of Sciences as a statutory activity and
AGH-University of Science and Technology (grant No 1111140199)
REFERENCES
[1] AUDRY S GROSBOIS C BRIL H SCHAFER J KIERCZAK J BLANC G Post-depositional redistribution
of trace metals in reservoir sediments of a miningsmelting-impacted watershed (the Lot River SW
France) Appl Geochem 2010 25 778
[2] CISZEWSKI D KUBSIK U ALEKSANDER-KWATERCZAK U Long-term dispersal of heavy metals in
a catchment affected by historic lead and zinc mining J Soils Sediments 2012 12 1445
[3] MUumlLLER J RUPPERT H MURAMATSU Y SCHNEIDER J Reservoir sediments A witness of mining and
industrial development (Malter Reservoir eastern Erzgebirge Germany) Environ Geol 2000
39(12) 1341
[4] CISZEWSKI D ALEKSANDER-KWATERCZAK U POCIECHA A SZAREK-GWIAZDA E WALOSZEK A
WILK-WOŹNIAK E Small effects of a large sediments contamination with heavy metals on aquatic
organisms in the vicinity of an abandoned lead and zinc mine Environ Monit Assess 2013 185
9825
[5] EC MENVIQ (Environmental Canada and Ministere de lrsquoEnvironment du Cuebec) Interim criteria
for quality assessment of St Lawrence River sediment Environment Canada Ottawa 1992
[6] CHENG S GROSSE W KARRENBROCK F THOENNESSEN M Efficiency of constructed wetlands in de-
contamination of water polluted by heavy metals Ecol Eng 2002 18 317
[7] CALMANO W VON DER KAMMER F SCHWARTZ R Characterization of redox conditions in soils and
sediments heavy metals [in] P Lens T Grotenhuis G Malina H Tabak (Eds) Soil and Sediment
Remediation IWA Publ London 2005 102ndash120
[8] CAPPUYNS V SWENNEN R Kinetics of element release during combined oxidation and pH stat leach-
ing of anoxic river sediments Appl Geochem 2005 20 1169
[9] MONCUR MC PTACEK CJ BLOWES DW JAMBOR J Release transport and attenuation of metals
from an old tailings impoundment Appl Geochem 2005 20 639
[10] WILK-WOŹNIAK E POCIECHA A CISZEWSKI D ALEKSANDER-KWATERCZAK U WALUSIAK E Phyto-
and zooplankton in fishponds contaminated with heavy metal runoff from a lead-zinc mine Oceanol
Hydrobiol Stud 2011 40 77
[11] MICHAILOVA P WARCHAŁOWSKA-ŚLIWA E SZAREK-GWIAZDA E KOWNACKI A Does biodiversity
of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal
pollution in a small pond Environ Monit Assess 2012 184 1
[12] ALEKSANDER-KWATERCZAK U CISZEWSKI D Groundwater hydrochemistry and soil pollution in
a catchment affected by an abandoned lead-zinc mine functioning of a diffuse pollution source
Environ Earth Sci 2012 65 1179
[13] SZAREK-GWIAZDA E Factors influencing the concentrations of heavy metals in the Raba River and
selected Carpathian dam Studia Naturae 2013 60 1 (in Polish)
[14] CABAŁA J Development of oxidation in ZnndashPb deposits in Olkusz area [in] Mineral Deposits at the
Beginning of the 21st Century Balkema 2001 121ndash124
[15] BUTLER TW II Geochemical and biological controls in trace metal transport in an acid mine im-
pacted watershed Environ Geochem Health 2006 28 231
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159
136 E SZAREK-GWIAZDA D CISZEWSKI
[16] STUMM W MORGAN JJ Aquatic chemistry Chemical equilibria and rates in natural waters Wiley
New York 1996
[17] SZAREK-GWIAZDA E ŻUREK R Distribution of trace elements in meromictic pit lake Water Air Soil
Pollut 2006 174 181
[18] TAILLEFERT M GAILLARD JF Reactive transport modeling of trace elements in the water column of
a stratified lake iron cycling and metal scavenging J Hydrol 2002 256 16
[19] WEBSTER JG SWEDLUNG PJ WEBSTER KS Trace element adsorption onto an acid mine drainage
iron(III) oxy-hydroxy sulfate Environ Sci Technol 1998 32 1361
[20] AVERHOFF OL GOacuteMEZ AB DEL REY ED AGUIAR CB VILLAZOacuteN MA Chemical physical and bio-
logical characteristics of Saladito Reservoir Cienfuegos Province Cuba Lakes Res Res Manage
2007 12 43
[21] LINNIK PM Zinc lead and cadmium speciation in Dnieper water-bodies Lakes Res Res Manage
2000 5 261
[22] MCDOWELL WH LIKENS GE Origin composition and flux of dissolved organic carbon in the Hub-
bard Brook Valley Ecol Monogr 1988 58 177
[23] JACKSON LJ Paradigms of metal accumulation in rooted aquatic vascular plants Sci Tot Environ
1998 219 223
[24] LI G XUE P YAN C LI Q Copper biosorption by Myriophyllum spicatum Effects of temperature
and pH Korean J Chem Eng 2010 27 (4) 1239
[25] KESKINKAN O GOKSU MZL YUCEER A BASIBUYUK M Comparison of the adsorption capabilities
of Myriophyllum spicatum and Ceratophyllum demersum for zinc copper and lead Eng Life Sci
2007 7 192
[26] SZYMCZYK S GRABIŃSKA B KOC-JURCZYK J Concentrations of Zn Pb Cu Cd and Ni in the waters
of the Narew river and some of its tributaries J Elementol 2007 12 199
[27] SUSCHKA J RYBOSZ S LESZCZYNSKA I Surface water and sediment contamination in an old indus-
trial region of Poland ndash two critical examples Water Sci Technol 1994 29 107
[28] MILOVANOVIC M Water quality assessment and determination of pollution sources along the
AxiosVardar River Southeastern Europe Desalination 2007 213 159